JP7467360B2 - Method for producing aromatic compounds from biomass - Google Patents

Description

The present invention relates to a method for producing aromatic compounds, which comprises reacting a mixture containing ethylene and a furan compound on a zeolitic material having a BEA-type framework structure, in which the zeolitic material having a BEA-type framework structure contained in the catalyst can be obtained and/or is obtained by a synthesis method that does not use an organic template.

The sustainable production of widely used bulk chemicals from biomass has attracted considerable attention due to the high costs, market volatility, and impending depletion of petroleum-based feedstocks. p-Xylene (PX) is one of the most important particular chemicals due to its widespread use for the production of terephthalic acid (TA), polyethylene terephthalate (PET), and subsequent synthesis of polyesters, synthetic fibers, plastic bottles, etc. Recently, a promising route for renewable p-Xylene production using the Diels-Alder reaction between ethylene and 2,5-dimethylfuran (2,5-DMF) has been proposed (see Figure 1). Notably, both 2,5-DMF and ethylene can be derived from biomass, offering the possibility of reducing the dependency on petroleum for their production.

US2013/0245316A1 relates to a method for producing p-xylene from renewable sources and ethylene in the presence of Lewis acid compounds as catalysts. Ni, L. et al. ChemSusChem2017,10,2394 relates to the synthesis of p-xylene from bio-based 2,5-dimethylfuran using metal triflates. Chang, C. -C. et al. Green Chem. 2014,16,585 relates to the cycloaddition reaction of biomass-derived ethylene and dimethylfuran with H-zeolite beta. Cho, H. J. et al. ChemCatChem2017,9,398 relates to renewable p-xylene from 2,5-dimethylfuran and ethylene using phosphorus-containing zeolite beta catalyst.

Although methods exist for preparing aromatics from biomass, there remains a need to optimize the conversion, especially with regard to reaction activity and selectivity.

US2013/0245316A1

Ni, L. et al. ChemSusChem 2017, 10, 2394 Chang, C.-C. et al. Green Chem. 2014, 16, 585 Cho, H. J. et al. ChemCatChem 2017, 9, 398

The object of the present invention is to provide an improved process for the production of aromatic compounds from biomass, and in particular an improved process for obtaining aromatic products via Diels-Alder cycloaddition reaction of alkylenes with furans or alkylated derivatives thereof, followed by removal of water. It has thus surprisingly been found that an improved process is provided, in particular with regard to the activity and selectivity of the reaction, by using a catalyst comprising a zeolitic material with a BEA-type framework structure obtained from an organic template-free synthesis.

The present invention therefore provides a method for producing an aromatic compound, comprising the steps of:
(1) Ethylene and formula (I)
preparing a mixture (M1) comprising a compound of
(2) feeding the mixture (M1) into a reactor containing a catalyst, the catalyst comprising a zeolitic material having a BEA-type framework structure;
(3) reacting at least a portion of the mixture (M1) to form a compound represented by formula (II)
contacting the mixture (M1) with a catalyst in a reactor to obtain aromatic compounds of
(4) recovering the reaction mixture (M2) containing the aromatic compound of formula (II) from the reactor;
Regarding the method,
wherein R ¹ and R ² independently of each other represent H or substituted or unsubstituted (C ₁ -C ₃ ) alkyl, preferably H or substituted or unsubstituted (C ₁ -C ₂ ) alkyl, more preferably H or substituted or unsubstituted methyl, and more preferably H or unsubstituted methyl; and the zeolitic material with BEA-type framework structure contained in the catalyst is obtainable and/or obtained by a synthesis method without the use of an organic template.

FIG. 1 shows a reaction scheme in which 2,5-dimethylfuran (2,5-DMF) undergoes a Diels-Alder cycloaddition reaction with ethylene to a cycloaddition intermediate that is converted to p-xylene by elimination of water. FIG. 2 shows a reaction scheme in which 2-methylfuran undergoes a Diels-Alder cycloaddition reaction with ethylene to a cycloaddition intermediate that is converted to toluene upon elimination of water. FIG. 3 shows a reaction scheme in which furan undergoes a Diels-Alder cycloaddition reaction with ethylene to form a cycloaddition intermediate that is converted to benzene with elimination of water. FIG. 4 shows the reaction products and selectivities in the conversion of 2,5-dimethylfuran and ethylene over zeolite beta catalysts for Reference Example 1, Reference Example 2, Reference Example 3, and commercial zeolite beta. FIG. 5 shows the reaction products and selectivities for the conversion of ethylene and 2,5-dimethylfuran (2,5-DMF), 2-methylfuran (2-MF), and furan, respectively, over a zeolite beta catalyst according to Example 2.

No particular restrictions apply with regard to the physical and/or chemical properties, e.g. XRD pattern, of the zeolitic material with a BEA-type framework structure contained in the catalyst. The zeolitic material with a BEA-type framework structure contained in the catalyst preferably exhibits an X-ray diffraction pattern including at least the following reflections:
Here, 100% means the intensity of the highest peak in the 2θ range of 20-45° in the X-ray powder diffraction pattern, and the BEA-type framework structure comprises SiO ₂ and X ₂ O ₃ , where X is a trivalent element.

As disclosed above, R ¹ and R ² independently of each other represent H or substituted or unsubstituted (C ₁ -C ₃ ) alkyl, preferably H or substituted or unsubstituted (C ₁ -C ₂ ) alkyl, more preferably H or substituted or unsubstituted methyl, and more preferably H or unsubstituted methyl. It is preferred that R ¹ and R ² independently of each other represent substituted or unsubstituted (C ₁ -C ₃ ) alkyl, more preferably substituted or unsubstituted (C ₁ -C ₂ ) alkyl, more preferably substituted or unsubstituted methyl, more preferably unsubstituted methyl.

With regard to ^R1 and ^R2 , it is particularly preferred that ^R1 represents H and ^R2 represents substituted or unsubstituted ( _C1 - _C3 ) alkyl, more preferably substituted or unsubstituted ( _C1 - _C2 ) alkyl, more preferably substituted or unsubstituted methyl, and more preferably unsubstituted methyl.

As disclosed above, the mixture (M1) is a mixture of ethylene and a cyclic olefin having the formula (I)
and

The compound of formula (I) is preferably selected from the group consisting of substituted or unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, more preferably from the group consisting of unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, and more preferably, the compound of formula (I) is 2-methylfuran and/or 2,5-dimethylfuran, preferably 2,5-dimethylfuran.

Regarding the molar ratio of ethylene to the compound of formula (I), no particular restrictions apply. The molar ratio of ethylene to the compound of formula (I) in the mixture (M1) prepared in step (1) and reacted in step (3) is preferably in the range of 0.01 to 1.5, more preferably 0.05 to 1, more preferably 0.08 to 0.7, more preferably 0.1 to 0.5, more preferably 0.12 to 0.3, more preferably 0.14 to 0.2, and more preferably 0.16 to 0.18.

Therefore, particularly preferably, the compound of formula (I) is selected from the group consisting of substituted or unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, more preferably from the group consisting of unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, where more preferably, the compound of formula (I) is 2-methylfuran and/or 2,5-dimethylfuran, preferably 2,5-dimethylfuran, and the molar ratio of ethylene:compound of formula (I) in the mixture (M1) prepared in step (1) and reacted in step (3) is in the range of 0.01 to 1.5, more preferably 0.05 to 1, more preferably 0.08 to 0.7, more preferably 0.1 to 0.5, more preferably 0.12 to 0.3, more preferably 0.14 to 0.2, and more preferably 0.16 to 0.18.

No special restrictions apply to the mixture (M1) prepared in step (1) and reacted in step (3), and further components, such as water, may be included therein. It is preferred that the mixture (M1) prepared in step (1) and reacted in step (3) contains 5% by weight or less of water based on 100% by weight of the compound of formula (I), more preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less. Particularly preferably, the mixture (M1) prepared in step (1) and reacted in step (3) contains substantially no water.

As disclosed above, no special restrictions apply to the mixture (M1) prepared in step (1) and reacted in step (3), which may contain further components, such as a solvent system. The mixture (M1) prepared in step (1) and reacted in step (3) preferably further comprises a solvent system, where the solvent system preferably comprises one or more solvents selected from the group consisting of butane, pentane, hexane, heptane, octane, nonane, decane, and mixtures of two or more thereof, more preferably from the group consisting of pentane, hexane, heptane, octane, nonane, and mixtures of two or more thereof, more preferably from the group consisting of hexane, heptane, octane, and mixtures of two or more thereof, more preferably the solvent system comprises heptane, more preferably the solvent system consists of heptane.

When the mixture (M1) prepared in step (1) and reacted in step (3) further comprises a solvent system, it is preferred that the mixture (M1) prepared in step (1) and reacted in step (3) contains a solution of the compound of formula (I) in the solvent system, where the concentration of the compound of formula (I) in the solvent system is in the range of 0.1-5M, 0.5-3M, more preferably 1-2.5M, more preferably 1.3-2M, more preferably 1.4-1.7M, and more preferably 1.5-1.6M.

Therefore, it is particularly preferred that the mixture (M1) prepared in step (1) and reacted in step (3) further comprises a solvent system, where the solvent system comprises one or more solvents selected from the group consisting of butane, pentane, hexane, heptane, octane, nonane, decane, and mixtures of two or more thereof, more preferably from the group consisting of pentane, hexane, heptane, octane, nonane, and mixtures of two or more thereof, more preferably from the group consisting of hexane, heptane, octane, and mixtures of two or more thereof, more preferably the solvent system comprises heptane, more preferably the solvent system consists of heptane, and the mixture (M1) prepared in step (1) and reacted in step (3) further comprises a solvent system for the compound of formula (I). The liquid is contained in a solvent system, wherein the concentration of the compound of formula (I) in the solvent system is in the range of 0.1 to 5M, 0.5 to 3M, more preferably 1 to 2.5M, more preferably 1.3 to 2M, more preferably 1.4 to 1.7M, and more preferably 1.5 to 1.6M, and the compound of formula (I) is selected from the group consisting of substituted or unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, more preferably from the group consisting of unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, and wherein more preferably the compound of formula (I) is 2-methylfuran and/or 2,5-dimethylfuran, preferably 2,5-dimethylfuran.

No particular restrictions apply to the partial pressure of ethylene in the reactor to which mixture (M1) is supplied in step (2) and to which the catalyst is contacted in step (3). The partial pressure of ethylene in the reactor to which mixture (M1) is supplied in step (2) and to which the catalyst is contacted in step (3) is preferably in the range of 0.5 to 15, more preferably 0.5 to 15 MPa, more preferably 1 to 10 MPa, more preferably 2 to 8 MPa, more preferably 2.5 to 6 MPa, more preferably 3 to 5 MPa, and more preferably 3.5 to 4.5 MPa, measured at 25°C.

No particular restrictions apply regarding the origin of the compound of formula (I) and/or ethylene, which may be derived from natural or synthetic methods. It is preferred that the compound of formula (I) and/or ethylene, preferably the compound of formula (I) and ethylene, are derived from biomass.

As disclosed above, no special restrictions apply with respect to the zeolite material having a BEA-type framework structure contained in the catalyst. In steps (2) and (3), the zeolite material having a BEA-type framework structure contained in the catalyst is preferably H-type.

As disclosed above, no particular restrictions apply with regard to the zeolitic material having a BEA-type framework structure contained in the catalyst, further components may be included therein, such as one or more metals, preferably one or more alkali metals and alkaline earth metals. In steps (2) and (3), the zeolite material having a BEA-type framework structure contained in the catalyst preferably contains 5% by mass or less of a metal AM, calculated as an element and based on 100% by mass of SiO ₂ contained in the framework structure of the zeolite material having a BEA-type framework structure, preferably 1% by mass or less, more preferably 0.5% by mass or less, more preferably 0.1% by mass or less, more preferably 0.05% by mass or less, more preferably 0.01% by mass or less, more preferably 0.005% _by mass or less, more preferably 0.001% by mass or less, more preferably 0.0005% by mass or less, and more preferably 0.0001% by mass or less, calculated as an element and based on 100% by mass of SiO 2 contained in the framework structure of the zeolite material having a BEA-type framework structure, where the metal AM represents Na, preferably Na and K, more preferably an alkali metal, and more preferably an alkali and alkaline earth metal.

As disclosed above, no particular restrictions apply with regard to the zeolitic material having a BEA-type framework structure contained in the catalyst, further components may be included therein, such as one or more metals, preferably one or more transition metals. In steps (2) and (3), the zeolite material having a BEA-type framework structure contained in the catalyst preferably contains 5% by mass or less of metal TM, calculated as an element and based on 100% by mass of SiO ₂ contained in the framework structure of the zeolite material having a BEA-type framework structure, preferably 1% by mass or less, more preferably 0.5% by mass or less, more preferably 0.1% by mass or less, more preferably 0.05% by mass or less, more preferably 0.01% by mass or less, more preferably 0.005% _by mass or less, more preferably 0.001% by mass or less, more preferably 0.0005% by mass or less, and more preferably 0.0001% by mass or less, calculated as an element and based on 100% by mass of SiO 2 contained in the framework structure of the zeolite material having a BEA-type framework structure, where metal TM represents Pt, Pd, Rh, and Ir, and preferably represents a transition metal element of Groups 3 to 12.

With regard to the catalyst contained in the reactor, no special restrictions apply, and further components, such as one or more metals, preferably one or more alkali metals and alkaline earth metals, may be contained therein. In steps (2) and (3), the catalyst in the reactor preferably contains, calculated as element, 5% by weight or less of metal AM based on 100% by weight of catalyst, more preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less of metal AM, calculated as element, based on 100% by weight of catalyst, where metal AM represents Na, preferably Na and K, more preferably alkali metals, and more preferably alkali and alkaline earth metals.

As disclosed above, no special restrictions apply with respect to the catalyst contained in the reactor, and further components, such as one or more metals, preferably one or more transition metals, may be contained therein. The catalyst contained in the reactor preferably contains 5% by weight or less of metal TM, calculated as element, based on 100% by weight of catalyst, preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less, calculated as element, based on 100% by weight of catalyst, where metal TM represents Pt, Pd, Rh, and Ir, and preferably represents a transition metal element of groups 3 to 12.

As disclosed above, no special restrictions are applied with respect to the zeolite material having a BEA-type framework structure contained in the catalyst, and further components, such as phosphorus, may be contained therein. In steps (2) and (3), it is preferred that the zeolite material having a BEA-type framework structure contained in the catalyst contains, calculated as an element, 5% by weight or less of phosphorus based on 100% by weight of SiO ₂ contained in the framework structure of the zeolite material having a BEA-type framework structure, more preferably, calculated as an element, 1% by weight or less of phosphorus based on 100% by weight of SiO ₂ contained in the framework structure of the zeolite material having a BEA-type framework structure, more preferably, 0.5 ...

As disclosed above, no special restrictions apply with regard to the catalyst contained in the reactor, and further components, such as phosphorus, may be included therein. In steps (2) and (3), the catalyst preferably contains 5% by weight or less of phosphorus, calculated as element, based on 100% by weight of catalyst, more preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less of metal AM, calculated as element, based on 100% by weight of catalyst.

No particular restrictions apply with respect to the contact of mixture (M1) with the catalyst in step (3), and any suitable conditions, for example in terms of temperature, may be applied. The contact of mixture (M1) with the catalyst in step (3) is preferably carried out at a temperature in the range of 150 to 350°C, more preferably 200 to 330°C, more preferably 230 to 320°C, more preferably 250 to 315°C, more preferably 270 to 310°C, more preferably 280 to 305°C, and more preferably 290 to 300°C.

As disclosed above, no particular restrictions apply with respect to the contact of mixture (M1) with the catalyst in step (3), and any suitable conditions, for example in terms of duration, may be applied. The duration of contact of mixture (M1) with the catalyst in step (3) is preferably in the range of 0.5 to 70 hours, more preferably 1 to 50 hours, more preferably 3 to 40 hours, more preferably 5 to 35 hours, more preferably 10 to 30 hours, more preferably 15 to 25 hours, more preferably 18 to 23 hours, and more preferably 19 to 21 hours.

Therefore, it is particularly preferred that the contact of mixture (M1) with the catalyst in step (3) is carried out at a temperature in the range of 150 to 350°C, more preferably 200 to 330°C, more preferably 230 to 320°C, more preferably 250 to 315°C, more preferably 270 to 310°C, more preferably 280 to 305°C, and more preferably 290 to 300°C, and that the contact period of mixture (M1) with the catalyst in step (3) is in the range of 0.5 to 70 hours, more preferably 1 to 50 hours, more preferably 3 to 40 hours, more preferably 5 to 35 hours, more preferably 10 to 30 hours, more preferably 15 to 25 hours, more preferably 18 to 23 hours, and more preferably 19 to 21 hours.

As disclosed above, no particular restrictions apply with respect to the contact of mixture (M1) with the catalyst in step (3) and the recovery of reaction mixture (M2) in step (4), and any suitable conditions, for example in terms of reaction mode, may be applied. It is preferred that the contact of mixture (M1) with the catalyst in step (3) and the recovery of reaction mixture (M2) in step (4) are carried out in continuous mode and/or batch mode, more preferably in batch mode.

No particular restrictions apply with regard to the reaction mode in which the method is carried out. It is preferred to carry out the method in continuous mode and/or batch mode, preferably in batch mode.

As disclosed above, the method for producing an aromatic compound comprises steps (1), (2), (3) and (4). With respect to said method, no special restrictions apply in terms of the process steps, and further process steps may be included therein. The method further comprises:
(5) It is preferable to further include a step of separating the compound of formula (II) from the reaction mixture (M2) to obtain a mixture (M3) containing the unreacted compound of formula (I) and/or unreacted ethylene.

As disclosed above, when the method includes step (5), again no special restrictions apply in terms of the method steps, and further method steps may be included therein.
(6) It is preferable to further include a step of recycling the mixture (M3) containing the unreacted compound of formula (I) and/or unreacted ethylene to the step (1).

As disclosed above, no particular restrictions apply with regard to the zeolitic material with a BEA-type framework structure contained in the catalyst. It is preferred that the zeolitic material with a BEA-type framework structure contained in the catalyst exhibits a SiO 2 :X 2 O 3 molar ratio in the range of 10-200, more preferably 15-150, more preferably 20-100, more preferably 25-70, more preferably 30-65, more preferably 35-60, more preferably 38-55, more preferably 40-50, and more preferably 42-46, whereby preferably the SiO ₂ :X ₂ O ₃ molar ratio of the framework structure is determined from elemental analysis or ²⁹ Si MAS NMR _of the zeolitic material, preferably from ²⁹ Si MAS NMR of the zeolitic material. Preferably, the SiO ₂ : _{X 2 O 3} molar ratio of the _framework structure is determined by ²⁹ Si MAS NMR according to the method described in the experimental section.

No special restrictions are applied to the trivalent element X of the zeolite material having a BEA-type framework structure contained in the catalyst. The trivalent element X of the zeolite material having a BEA-type framework structure contained in the catalyst is preferably selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, more preferably from the group consisting of Al, Ga, and mixtures thereof, and X is more preferably Al.

As disclosed above, no particular restrictions apply with respect to the zeolitic material with a BEA-type framework structure contained in the catalyst. It is preferred that the zeolitic material with a BEA-type framework structure contained in the catalyst exhibits an amount of Bronsted acid sites (BA) in the range of 100-900 μmol/g, more preferably 150-700 μmol/g, more preferably 200-650 μmol/g, more preferably 350-600 μmol/g, more preferably 380-550 μmol/g, more preferably 410-500 μmol/g, more preferably 430-470 μmol/g, and more preferably 445-450 μmol/g, where the amount of Bronsted acid sites is determined by temperature programmed ammonia desorption (NH3-TPD) or ³¹ P MAS NMR using trimethylphosphine oxide. Preferably, the amount of Bronsted acid sites is determined according to the method described in the experimental section.

As disclosed above, no particular restrictions apply with regard to the zeolitic material with a BEA-type framework structure contained in the catalyst. It is preferred that the zeolitic material with a BEA-type framework structure contained in the catalyst exhibits an amount of Lewis acid sites (LA) in the range of 100-350 μmol/g, more preferably 110-300 μmol/g, more preferably 120-280 μmol/g, more preferably 140-260 μmol/g, more preferably 150-240 μmol/g, more preferably 160-220 μmol/g, more preferably 170-200 μmol/g, and more preferably 180-190 μmol/g, where the amount of Lewis acid sites is determined by temperature programmed desorption of ammonia (NH3-TPD) or ³¹ P MAS NMR using trimethylphosphine oxide. Preferably, the amount of Lewis acid sites is determined according to the method described in the experimental section.

Thus, it is particularly preferred that the zeolitic material with a BEA-type framework structure contained in the catalyst exhibits an amount of Brønsted acid sites (BA) in the range of 100-900 μmol/g, more preferably 150-700 μmol/g, more preferably 200-650 μmol/g, more preferably 350-600 μmol/g, more preferably 380-550 μmol/g, more preferably 410-500 μmol/g, more preferably 430-470 μmol/g and more preferably 445-450 μmol/g, wherein the amount of Brønsted acid sites can be determined by temperature programmed ammonia desorption (NH3-TPD) or ³¹ P MAS using trimethylphosphine oxide. The zeolitic material having a BEA-type framework structure as determined by NMR and contained in the catalyst exhibits an amount of Lewis acid sites (LA) in the range of 100-350 μmol/g, more preferably 110-300 μmol/g, more preferably 120-280 μmol/g, more preferably 140-260 μmol/g, more preferably 150-240 μmol/g, more preferably 160-220 μmol/g, more preferably 170-200 μmol/g, and more preferably 180-190 μmol/g, wherein the amount of Lewis acid sites is determined by temperature programmed ammonia desorption (NH3-TPD) or ³¹ P MAS NMR using trimethylphosphine oxide.

Furthermore, it is particularly preferred that the zeolitic material having a BEA-type framework structure contained in the catalyst has a BA:LA ratio of the amount of Bronsted acid sites (BA) to the amount of Lewis acid sites (LA) in the range of from 0.5 to 8, preferably from 1 to 5, more preferably from 1.3 to 4, more preferably from 1.6 to 3.4, more preferably from 1.8 to 3, more preferably from 2.0 to 2.7, more preferably from 2.2 to 2.6, and more preferably from 2.3 to 2.5, wherein the amount of Bronsted acid sites and Lewis acid sites, respectively, are determined by temperature programmed ammonia desorption (NH3-TPD) or by ^31P MAS NMR using trimethylphosphine oxide.

No particular restrictions apply with regard to the physical and/or chemical properties, such as the BET surface area, of the zeolitic material having a BEA-type framework structure contained in the catalyst. It is preferred that the BET surface area, determined according to ISO 9277:2010, of the zeolitic material having a BEA-type framework structure contained in the catalyst is in the range of 350-800 m ² /g, more preferably 400-700 m ² /g, more preferably 430-650 m ² /g, more preferably 450-600 m ² /g, more preferably 460-550 m ² /g, more preferably 470-530 m ² /g, more preferably 480-520 m ² /g, and more preferably 490-510 m ² /g.

No particular restrictions apply with regard to the physical and/or chemical properties, such as the total pore volume, of the zeolitic material having a BEA-type framework structure contained in the catalyst. It is preferred that the total pore volume of the zeolitic material having a BEA-type framework structure contained in the catalyst, determined by nitrogen adsorption from the BJH method, is in the range of 0.3-0.5 cm/g, preferably 0.31-0.45 ^cm /g, more preferably 0.32-0.42 ^cm /g, more preferably 0.33-0.4 ^cm /g, more preferably 0.34-0.39 ^cm /g, more preferably 0.35-0.38 ^cm /g, and more preferably 0.36-0.37 ^cm /g, where the total pore volume is preferably determined according to DIN 66134.

No particular restrictions apply with regard to the organic template-free synthesis method by which the zeolitic material with BEA-type framework structure contained in the catalyst can be obtained and/or obtained. The organic template-free synthesis method can be
(A) preparing a mixture comprising one or more sources of _SiO2 , one or more sources of _X2O3 , and seed _crystals , the seed crystals comprising one or more zeolitic materials having a BEA-type framework structure;
(B) It is preferred to include a step of crystallizing the mixture obtained in step (A) in order to obtain a zeolitic material having a BEA-type framework structure, where X is a trivalent element, and the mixture prepared in step (A) and crystallized in step (B) does not contain an organic template as a structure directing agent.

When the method includes an organic template-free synthesis method comprising steps (A) and (B) as disclosed above, no special restrictions are applied with respect to the mixture prepared in step (A) and crystallized in step (B), which may contain further components, such as carbon. It is preferred that the mixture prepared in step (A) and crystallized in step (B) contains 5% by weight or less of carbon, calculated as element and based on 100% by weight of SiO ₂ contained in the _mixture , more preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less.

When the method comprises an organic template-free synthesis comprising steps (A) and (B) as disclosed above, no special restrictions apply with respect to the zeolitic material having a BEA-type framework structure obtained in step (B), which may comprise further components, for example one or more alkali metals M. It is preferred that the zeolitic material having a BEA-type framework structure obtained in step (B) comprises one or more alkali metals M, where M is preferably selected from the group consisting of Li, Na, K, Cs, and combinations of two or more thereof, more preferably from the group consisting of Li, Na, K, and combinations of two or more thereof, more preferably the alkali metal M is Na and/or K, more preferably Na.

When the zeolitic material with a BEA-type framework structure obtained in step (B) contains one or more alkali metals M as disclosed above, no special restrictions apply with regard to the molar ratio M: _SiO2 in the mixture prepared in step (A) and crystallized in step (B). It is preferred that the molar ratio M: _SiO2 in the mixture prepared in step (A) and crystallized in step (B) is in the range of 0.05 to 5, more preferably 0.1 to 2, more preferably 0.3 to 1, more preferably 0.4 to 0.8, more preferably 0.45 to 0.7, more preferably 0.5 to 0.65, and more preferably 0.55 to 0.6.

When the method includes an organic template-free synthesis method comprising steps (A) and (B) as disclosed above, no special restrictions apply with respect to the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B). The one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) preferably comprise one or more silicates, preferably one or more alkali metal silicates, where the alkali metal is more preferably selected from the group consisting of Li, Na, K, Rb, and Cs, more preferably the alkali metal is Na and/or K, and more preferably the alkali metal is Na, and where the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) preferably comprise water glass, preferably sodium silicate and/or potassium silicate, more preferably sodium silicate.

When the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) comprise one or more silicates as disclosed above, no special restrictions apply in terms of the further components contained therein. It is preferred that the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) further comprise one or more silicas, more preferably one or more silica hydrosols and/or one or more colloidal silicas, and more preferably one or more colloidal silicas.

Therefore, particularly preferred, when the method comprises an organic template-free synthesis comprising steps (A) and (B) as disclosed above, the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) comprise one or more silicates, preferably one or more alkali metal silicates, where the alkali metal is more preferably selected from the group consisting of Li, Na, K, Rb and Cs, more preferably the alkali metal is Na and/or K, and more preferably the alkali metal is Na, and more preferably the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) comprise water glass, preferably sodium silicate and/or potassium silicate, more preferably sodium silicate, and the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) further comprise one or more silicas, more preferably one or more silica hydrosols and/or one or more colloidal silicas, and more preferably one or more colloidal silicas.

When the method includes an organic template-free synthesis method comprising steps (A) and (B) as disclosed above, no special restrictions apply regarding X, so long as it is a trivalent element as disclosed above. X is preferably selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, more preferably from the group consisting of Al, Ga, and mixtures thereof, and X is more preferably Al.

When the method comprises an organic template-free synthesis comprising steps (A) and (B) as disclosed above, no special restrictions apply with respect to the one or more sources of _X2O3 contained in the mixture prepared in step (A) _and crystallized in step (B). The one or more sources of _X2O3 contained in the mixture prepared in step (A) and crystallized in step (B) preferably comprise _one or more aluminate salts, preferably aluminates of alkali metals, where the alkali metals are preferably selected from the group consisting of Li, Na, K, Rb, and Cs, more preferably the alkali metals are Na and/or K, and more preferably the alkali metal is Na.

When the method comprises an organotemplate-free synthesis comprising steps (A) and (B) as disclosed above, no special restrictions apply with regard to the molar ratio SiO ₂ :X ₂ O ₃ of the mixture prepared in step (A) and crystallized in step (B). It is preferred that the molar ratio SiO ₂ :X ₂ O ₃ of the mixture prepared in step (A) and crystallized in step (B) is in the range of 1-200, more preferably 5-100, more preferably 10-50, more preferably 15-40, more preferably 20-30, more preferably 23-25, and more preferably 23.5-24.

When the method comprises an organic template-free synthesis comprising steps (A) and (B) as disclosed above, no special restrictions apply with respect to the mixture prepared in step (A) and crystallized in step (B), which may comprise further components, such as one or more solvents. It is preferred that the mixture prepared in step (A) and crystallized in step (B) further comprises one or more solvents, where said one or more solvents more preferably comprise water, more preferably deionized water, where more preferably water, preferably deionized water, is used as the solvent further comprised in the mixture prepared in step (A) and crystallized in step (B).

When the mixture prepared in step (A) and crystallized in step (B) further comprises one or more solvents as disclosed above, no special restrictions apply with respect to the molar ratio H ₂ O:SiO ₂ of the mixture prepared in step (A) and crystallized in step (B). It is preferred that the molar ratio H ₂ O:SiO ₂ of the mixture prepared in step (A) and crystallized in step (B) is in the range of 5-100, preferably 10-50, more preferably 13-30, more preferably 15-20, and more preferably 17-18.

When the method comprises an organic template-free synthesis comprising steps (A) and (B) as disclosed above, no special restrictions apply with respect to the conditions, e.g., the temperature of the mixture under which the crystallization of step (B) is carried out. The crystallization of step (B) preferably involves heating the mixture, more preferably at temperatures in the range of 80-200°C, more preferably 90-180°C, more preferably 100-160°C, more preferably 110-140°C, and more preferably 115-130°C.

When the method comprises an organic template-free synthesis comprising steps (A) and (B) as disclosed above, no special restrictions apply with respect to the conditions, e.g. the pressure, under which the crystallization of step (B) is carried out. It is preferred that the crystallization of step (B) is carried out under autogenous pressure, more preferably under solvothermal conditions, and more preferably under hydrothermal conditions.

Therefore, it is particularly preferred that the crystallization in step (B) involves heating the mixture, more preferably the temperature of heating is in the range of 80 to 200°C, more preferably 90 to 180°C, more preferably 100 to 160°C, more preferably 110 to 140°C, and more preferably 115 to 130°C, and that the crystallization in step (B) is carried out under autogenous pressure, more preferably under solvothermal conditions, and more preferably under hydrothermal conditions.

When the crystallization in step (B) involves heating the mixture as disclosed above and/or when the crystallization in step (B) is carried out under autogenous pressure as disclosed above, no special restrictions apply with respect to the period for which the mixture is heated in step (B). It is preferred to heat the mixture in step (B) for a period in the range of 5 to 200 hours, preferably 20 to 160 hours, more preferably 60 to 140 hours, and more preferably 100 to 130 hours.

When the method comprises an organotemplate-free synthesis method comprising steps (A) and (B) as disclosed above, no special restrictions apply with respect to the further process steps comprised therein.
(C) isolating the zeolitic material having a BEA-type framework structure obtained in step (B), preferably by filtration, and (D) optionally washing the zeolitic material having a BEA-type framework structure obtained in step (B) or (C), preferably in step (C), and/or
(E) optionally drying the zeolitic material having a BEA-type framework structure obtained in step (B), (C) or (D), preferably in step (D),
wherein steps (C) and/or (D) and/or (E) can be performed in any order, and wherein one or more of said steps are preferably repeated one or more times.

When the process comprises an organotemplate-free synthesis comprising steps (A), (B), (C), optionally step (D) and optionally step (E) as disclosed above, again no special restrictions apply with respect to the further process steps comprised therein. It is contemplated that the organotemplate-free synthesis for preparing a zeolitic material having a BEA-type framework structure comprises:
(F) in step (C), (D) or (E) exchanging one or more ionic non-framework elements contained in the zeolitic material with BEA-type framework structure preferably obtained in step (E) for H ⁺ and/or NH ₄ ⁺ , preferably for NH ₄ ⁺ ; and/or (G) preferably drying and/or calcining, preferably drying and calcining, the zeolitic material with BEA-type framework structure obtained in step (C), (D), (E) or (F),
Here, steps (F) and/or (G) are preferably repeated one or more times, preferably 1 to 3 times, more preferably 1 or 2 times, and more preferably 1 time.

When the process comprises an organotemplate-free synthesis comprising steps (A), (B), (C), optionally step (D), optionally step (E), and optionally steps (F) and (G) as disclosed above, no special restrictions apply as regards the further process steps comprised therein.
(H) in step (C), (D), (E), (F) or (G), preferably treating the zeolitic material having a BEA-type framework structure obtained in step (G) with an aqueous solution having a pH of at most 5, and (I) isolating the zeolitic material having a BEA-type framework structure obtained in step (H), preferably by filtration, and/or
(J) optionally washing the zeolitic material having a BEA-type framework structure obtained in step (H) or (I), preferably in step (I), and/or
(K) step (H), (I) or (J) preferably further comprises a step of optionally drying and/or calcining, preferably drying, the zeolitic material having a BEA-type framework structure preferably obtained in step (J);
wherein steps (I) and/or (J) and/or (K) can be performed in any order, and one or more of said steps are preferably repeated one or more times, preferably 1 to 3 times, more preferably 1 or 2 times, and more preferably once.

When the method comprises an organic template-free synthesis comprising steps (H), (I), optionally step (J), and optionally step (K) as disclosed above, no special restrictions apply with respect to the conditions, e.g., the pH of the aqueous solution used to treat the zeolitic material in step (H), so long as the pH of the aqueous solution is at most 5. It is preferred that the pH of the aqueous solution used to treat the zeolitic material in step (H) is in the range of -1.5 to 3, preferably -1.2 to 2, more preferably -1 to 1.5, more preferably -0.8 to 1, more preferably -0.6 to 0.7, more preferably -0.5 to 0.5, more preferably -0.3 to 0.3, more preferably -0.2 to 0.2, and more preferably -0.1 to 0.1.

Where the method comprises an organotemplate-free synthesis comprising steps (H), (I), optionally step (J) and optionally step (K) as disclosed above, no particular restrictions apply with respect to the nature of the aqueous solution used to treat the zeolitic material in step (H). It is preferred that in step (H) the zeolitic material is treated with an aqueous solution of a mineral acid. Furthermore, it is preferred that the concentration of the mineral acid in the aqueous solution is in the range of 0.05-4M, more preferably 0.1-3M, more preferably 0.2-2.5M, more preferably 0.4-2M, more preferably 0.6-1.5M, more preferably 0.8-1.2M and more preferably 0.9-1.1M.

As disclosed above, when a mineral acid is used in step (H), no particular restrictions apply with respect to the nature of the mineral acid. It is preferred that the mineral acid is selected from the group consisting of _HF , HCl, _HBr , _HNO3 , _H3PO4 , _{H2SO4 , H3BO3} , _HClO4 , and mixtures of two or more thereof, more preferably from the group consisting of HCl, HBr, _{HNO3 , H2SO4 , HClO4} , and mixtures of two _or more thereof, more preferably from the group consisting of HCl, _HNO3 , _H2SO4 , and mixtures of two or more thereof, where more preferably the mineral acid is HCl and/or _HNO3 , preferably _HNO3 .

Particularly preferably, therefore, in step (H) the zeolitic material is treated with an aqueous solution of a mineral acid. Further, it is preferred that the concentration of the mineral acid in the aqueous solution is in the range of 0.05-4M, more preferably 0.1-3M, more preferably 0.2-2.5M, more preferably 0.4-2M, more preferably 0.6-1.5M, more preferably 0.8-1.2M, and more preferably 0.9-1.1M, and that the mineral acid is selected from the group consisting of HF, HCl, HBr, HNO ₃ , H ₃ PO ₄ , H ₂ SO ₄ , H ₃ BO ₃ , HClO ₄ , and mixtures of two or more thereof, more preferably from the group consisting of HCl, HBr, HNO ₃ , H ₂ SO ₄ , HClO ₄ , and mixtures of two or more thereof, more preferably from the group consisting of HCl, HNO ₃ , H ₂ SO ₄ , and mixtures of two or more thereof, and more preferably the mineral acid is HCl and/or HNO ₃ , preferably HNO ₃ .

If the method comprises an organic template-free synthesis comprising steps (H), (I), optionally step (J) and optionally step (K) as disclosed above, no special restrictions apply as to the manner in which in steps (C), (D), (E), (F) or (G) the zeolitic material having a BEA-type framework structure, preferably obtained in step (G), is treated with an aqueous solution having a pH of at most 5. According to a first alternative, in step (H), it is preferred to add the zeolitic material to the aqueous solution and to heat the mixture at a temperature preferably in the range of 30 to 100°C, more preferably 35 to 90°C, more preferably 40 to 80°C, more preferably 45 to 75°C, more preferably 50 to 70°C and more preferably 55 to 65°C. According to a second alternative, in step (H), it is preferred to add the zeolite material to the aqueous solution and treat the mixture at a temperature in the range of 5 to 40°C, more preferably 10 to 35°C, more preferably 15 to 30°C, more preferably 17 to 25°C, more preferably 19 to 23°C, and more preferably 20 to 22°C.

When the method comprises an organic template-free synthesis comprising steps (H), (I), optionally step (J), and optionally step (K) as disclosed above, no particular restrictions apply with respect to the conditions, e.g., the period for which the mixture is treated in step (H). It is preferred to treat the mixture in step (H) for a period in the range of 0.1 to 10 hours, more preferably 0.1 to 7 hours, more preferably 0.5 to 5 hours, more preferably 0.5 to 4.5 hours, more preferably 1 to 4 hours, more preferably 1 to 3.5 hours, more preferably 1.5 to 3 hours, and more preferably 1.5 to 2.5 hours.

When the method comprises an organic template-free synthesis comprising at least steps (A), (B), (C), optionally step (D), and optionally step (E) as disclosed above, no particular restrictions apply with regard to the conditions, e.g. the temperature, at which drying in steps (E) and/or (G) and/or (K), preferably in steps (E), (G) and (K), is carried out. Drying in steps (E) and/or (G) and/or (K), preferably in steps (E), (G) and (K), is preferably carried out at a temperature in the range of 80-200°C, more preferably 90-180°C, more preferably 100-160°C, more preferably 110-140°C, and more preferably 115-130°C.

When the method comprises an organic template-free synthesis comprising at least steps (A), (B), (C), optionally step (D), and optionally step (E) as disclosed above, no special restrictions apply with respect to the conditions, e.g. the duration for which drying is carried out in steps (E) and/or (G) and/or (K), preferably in steps (E), (G) and (K). Drying in steps (E) and/or (G) and/or (K), preferably in steps (E), (G) and (K), is preferably carried out for a period in the range of 1 to 120 hours, preferably 5 to 96 hours, more preferably 8 to 72 hours, more preferably 10 to 60 hours, more preferably 12 to 48 hours, more preferably 14 to 42 hours, more preferably 16 to 36 hours, more preferably 18 to 30 hours, more preferably 20 to 24 hours, and more preferably 21 to 23 hours.

Thus, particularly preferably, when the method comprises an organic template-free synthesis comprising at least steps (A), (B), (C), optionally step (D), and optionally step (E) as disclosed above, the drying in steps (E) and/or (G) and/or (K), preferably in steps (E), (G) and (K), is carried out at a temperature in the range of 80 to 200°C, more preferably 90 to 180°C, more preferably 100 to 160°C, more preferably 110 to 140°C, and more preferably 115 to 130°C, and the drying in steps (E) and/or (G) and/or (K), preferably in steps (E), (G) and (K), is carried out for a period in the range of 1 to 120 hours, preferably 5 to 96 hours, more preferably 8 to 72 hours, more preferably 10 to 60 hours, more preferably 12 to 48 hours, more preferably 14 to 42 hours, more preferably 16 to 36 hours, more preferably 18 to 30 hours, more preferably 20 to 24 hours, and more preferably 21 to 23 hours.

When the method comprises an organic template-free synthesis comprising at least steps (F) and (G) as disclosed above, no special restrictions apply with respect to the conditions, e.g. the temperature of the calcination in steps (G) and/or (K) (if step (K) is applicable), where calcination is performed. Calcination in steps (G) and/or (K) (if step (K) is applicable), more preferably in step (G), is preferably performed at a temperature in the range of 250-1,000°C, preferably 300-900°C, more preferably 350-850°C, more preferably 400-800°C, more preferably 450-750°C, more preferably 500-700°C, and more preferably 550-650°C.

When the method comprises an organic template-free synthesis comprising at least steps (F) and (G) as disclosed above, no special restrictions apply with respect to the conditions, e.g. the duration of calcination in steps (G) and/or (K) (if step (K) is applicable), where calcination is performed. Calcination in steps (G) and/or (K) (if step (K) is applicable), more preferably in step (G), is preferably performed for a period in the range of 0.5 to 36 hours, more preferably 1 to 24 hours, more preferably 1.5 to 18 hours, more preferably 2 to 12 hours, more preferably 2.5 to 9 hours, more preferably 3 to 7 hours, more preferably 3.5 to 6.5 hours, more preferably 4 to 6 hours, and more preferably 4.5 to 5.5 hours.

Therefore, particularly preferably, when the method comprises an organic template-free synthesis comprising at least steps (F) and (G) as disclosed above, the calcination in steps (G) and/or (K) (if step (K) is applicable), more preferably in step (G), is carried out at a temperature in the range of 250-1,000°C, preferably 300-900°C, more preferably 350-850°C, more preferably 400-800°C, more preferably 450-750°C, more preferably 500-700°C, and more preferably 550-650°C, and the calcination in steps (G) and/or (K) (if step (K) is applicable), more preferably in step (G), is carried out for a period in the range of 0.5-36 hours, more preferably 1-24 hours, more preferably 1.5-18 hours, more preferably 2-12 hours, more preferably 2.5-9 hours, more preferably 3-7 hours, more preferably 3.5-6.5 hours, more preferably 4-6 hours, and more preferably 4.5-5.5 hours.

When the method comprises an organic template-free synthesis method comprising at least steps (A) and (B) as disclosed above, no special restrictions apply with respect to the physical and/or chemical properties of the zeolitic material having a BEA-type framework structure. It is preferred that the zeolitic material having a BEA-type framework structure formed in step (B) comprises zeolite beta, where preferably the zeolitic material having a BEA-type framework structure formed in step (B) is zeolite beta.

When the method comprises an organic template-free synthesis process comprising at least steps (A) and (B) as disclosed above, no special restrictions apply with respect to the physical and/or chemical properties of the seed crystals contained in the mixture prepared in step (A) and crystallized in step (B). It is preferred that the seed crystals contained in the mixture prepared in step (A) and crystallized in step (B) comprise a zeolitic material having a BEA-type framework structure, more preferably zeolite beta, and more preferably a zeolitic material having a BEA-type framework structure obtainable and/or obtainable by an organic template-free synthesis process for the production of a zeolitic material having a BEA-type framework structure as disclosed herein.

The present invention is further illustrated by the following embodiments and combinations of embodiments, as indicated by their respective dependencies and back references. In particular, in each instance where combinations of embodiments are referred to as ranges, it is noted that in the context of a term such as "the method according to any one of embodiments 1 to 4," all embodiments within this range are intended to be expressly disclosed to one of ordinary skill in the art, i.e., the wording of this term is understood by one of ordinary skill in the art to be equivalent to "the method according to any one of embodiments 1, 2, 3, and 4." Thus, the present invention includes the following embodiments, which include specific combinations of the embodiments as indicated by their respective interrelationships defined therein:

1. A method for producing an aromatic compound, comprising the steps of:
(1) Ethylene and formula (I)
preparing a mixture (M1) comprising a compound of
(2) feeding the mixture (M1) into a reactor containing a catalyst, the catalyst comprising a zeolitic material having a BEA-type framework structure;
(3) reacting at least a portion of the mixture (M1) to form a compound represented by formula (II)
contacting the mixture (M1) with a catalyst in a reactor to obtain aromatic compounds of
(4) recovering the reaction mixture (M2) containing the aromatic compound of formula (II) from the reactor;
Including,
wherein R ¹ and R ² independently of each other represent H or substituted or unsubstituted (C ₁ -C ₃ ) alkyl, preferably H or substituted or unsubstituted (C ₁ -C ₂ ) alkyl, more preferably H or substituted or unsubstituted methyl, and more preferably H or unsubstituted methyl; and wherein the zeolitic material with a BEA-type framework structure contained in the catalyst is obtainable and/or obtained by an organic template-free synthesis method.

2. Zeolitic materials having a BEA-type framework structure exhibit an X-ray diffraction pattern that includes at least the following reflections:

2. The method of embodiment 1, wherein 100% means the intensity of the highest peak in the 2θ range of 20-45° in the X-ray powder diffraction pattern; and wherein the BEA-type framework structure comprises _{SiO2 and X2O3} , where X is a trivalent element.

3. The method according to embodiment 1 or 2, wherein R ¹ and R ² , independently of each other, represent substituted or unsubstituted (C ₁ -C ₃ ) alkyl, preferably substituted or unsubstituted (C ₁ -C ₂ ) alkyl, more preferably substituted or unsubstituted methyl, more preferably unsubstituted methyl.

4. The method according to any one of embodiments 1 to 3, wherein R ¹ represents H and R ² represents substituted or unsubstituted (C ₁ -C ₃ ) alkyl, preferably substituted or unsubstituted (C ₁ -C ₂ ) alkyl, more preferably substituted or unsubstituted methyl, and more preferably unsubstituted methyl.

5. The method according to any one of embodiments 1 to 4, wherein the compound of formula (I) is selected from the group consisting of substituted or unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, preferably from the group consisting of unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof, and more preferably wherein the compound of formula (I) is 2-methylfuran and/or 2,5-dimethylfuran, preferably 2,5-dimethylfuran.

6. The method of any one of embodiments 1 to 5, wherein the molar ratio of ethylene to the compound of formula (I) in the mixture (M1) prepared in step (1) and reacted in step (3) is in the range of 0.01 to 1.5, preferably 0.05 to 1, more preferably 0.08 to 0.7, more preferably 0.1 to 0.5, more preferably 0.12 to 0.3, more preferably 0.14 to 0.2, and more preferably 0.16 to 0.18.

7. The method according to any one of embodiments 1 to 6, wherein the mixture (M1) prepared in step (1) and reacted in step (3) contains 5% or less by weight of water based on 100% by weight of the compound of formula (I), preferably 1% or less by weight, more preferably 0.5% or less by weight, more preferably 0.1% or less by weight, more preferably 0.05% or less by weight, more preferably 0.01% or less by weight, more preferably 0.005% or less by weight, more preferably 0.001% or less by weight, more preferably 0.0005% or less by weight, and more preferably 0.0001% or less by weight of water based on 100% by weight of the compound of formula (I).

8. The method according to any one of embodiments 1 to 7, wherein the mixture (M1) prepared in step (1) and reacted in step (3) further comprises a solvent system, wherein the solvent system preferably comprises one or more solvents selected from the group consisting of butane, pentane, hexane, heptane, octane, nonane, decane, and mixtures of two or more thereof, preferably from the group consisting of pentane, hexane, heptane, octane, nonane, and mixtures of two or more thereof, more preferably from the group consisting of hexane, heptane, octane, and mixtures of two or more thereof, more preferably the solvent system comprises heptane, more preferably the solvent system consists of heptane.

9. The method of embodiment 8, wherein the mixture (M1) prepared in step (1) and reacted in step (3) contains a solution of the compound of formula (I) in a solvent system, wherein the concentration of the compound of formula (I) in the solvent system ranges from 0.1 to 5 M, 0.5 to 3 M, more preferably from 1 to 2.5 M, more preferably from 1.3 to 2 M, more preferably from 1.4 to 1.7 M, and more preferably from 1.5 to 1.6 M.

10. The method according to any one of embodiments 1 to 9, wherein the partial pressure of ethylene in the reactor to which mixture (M1) is supplied in step (2) and to which the catalyst is contacted in step (3) is in the range of 0.5 to 15, preferably 0.5 to 15 MPa, more preferably 1 to 10 MPa, more preferably 2 to 8 MPa, more preferably 2.5 to 6 MPa, more preferably 3 to 5 MPa, and more preferably 3.5 to 4.5 MPa, measured at 25°C.

11. The method of any one of embodiments 1 to 10, wherein the compound of formula (I) and/or ethylene, preferably the compound of formula (I) and ethylene, are derived from biomass.

12. The method according to any one of embodiments 1 to 11, wherein in steps (2) and (3), the zeolite material having a BEA-type framework structure contained in the catalyst is H-type.

13. The method according to any one of the preceding embodiments, wherein in step (2) and step (3), the zeolite material having a BEA-type framework structure contained in the catalyst contains 5% by mass or less of metal AM, calculated as an element and based on 100% by mass of SiO ₂ contained in the framework structure of the zeolite material having a BEA-type framework structure, preferably 1% by mass or less, more preferably 0.5% by mass or less, more preferably 0.1% by mass or less, more preferably 0.05% _by mass or less, more preferably 0.01% by mass or less, more preferably 0.005% by mass or less, more preferably 0.001% by mass or less, more preferably 0.0005% by mass or less, and more preferably 0.0001% by mass or less, calculated as an element and based on 100% by mass of SiO 2 contained in the framework structure of the zeolite material having a BEA-type framework structure, wherein the metal AM represents Na, preferably Na and K, more preferably an alkali metal, and more preferably an alkali and alkaline earth metal.

14. In step (2) and step (3), the zeolite material having a BEA-type framework structure contained in the catalyst contains, calculated as an element, 5% or less by mass of metal TM based on 100% by mass of SiO ₂ contained in the framework structure of the zeolite material having a BEA-type framework structure, preferably, calculated as an element, 1% or less by mass of metal TM based on 100% by mass of SiO ₂ contained in the framework structure of the zeolite material having a BEA-type framework structure, more preferably 0.5 ...
14. The method of any one of the preceding embodiments, wherein the metal TM represents Pt, Pd, Rh, and Ir, and preferably represents a transition metal element of groups 3 to 12.

15. In step (2) and step (3), the catalyst in the reactor contains, calculated as element, 5% or less by weight of metal AM based on 100% by weight of catalyst, preferably, calculated as element, 1% or less by weight of metal AM based on 100% by weight of catalyst, more preferably 0.5% or less by weight, more preferably 0.1% or less by weight, more preferably 0.05% or less by weight, more preferably 0.01% or less by weight, more preferably 0.005% or less by weight, more preferably 0.001% or less by weight, more preferably 0.0005% or less by weight, and more preferably 0.0001% or less by weight;
15. The method according to any one of the preceding embodiments, wherein the metal AM represents Na, preferably Na and K, more preferably alkali metals, and more preferably alkali and alkaline earth metals.

16. The catalyst contained in the reactor contains 5% or less by weight of TM metals, calculated as element, based on 100% by weight of catalyst, preferably 1% or less by weight, calculated as element, based on 100% by weight of catalyst, more preferably 0.5% or less by weight, more preferably 0.1% or less by weight, more preferably 0.05% or less by weight, more preferably 0.01% or less by weight, more preferably 0.005% or less by weight, more preferably 0.001% or less by weight, more preferably 0.0005% or less by weight, and more preferably 0.0001% or less by weight;
16. The method of any one of the preceding embodiments, wherein the metal TM represents Pt, Pd, Rh, and Ir, and preferably represents a transition metal element of groups 3 to 12.

17. The method according to any one of embodiments 1 to 16, wherein in step (2) and step (3), the zeolite material having a BEA-type framework structure contained in the catalyst contains 5% by weight or less of phosphorus, calculated as the element and based on 100% by weight of _SiO2 contained in the framework structure of the zeolite material having a BEA-type framework structure, preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably _0.1 % by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less, calculated as the element and based on 100% by weight of SiO2 contained in the framework structure of the zeolite material having a BEA-type framework structure.

18. The method according to any one of embodiments 1 to 17, wherein in steps (2) and (3), the catalyst contains 5% by weight or less of phosphorus, calculated as element, based on 100% by weight of catalyst, and preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less of metal AM, calculated as element, based on 100% by weight of catalyst.

19. The method according to any one of embodiments 1 to 18, wherein the contact of mixture (M1) with the catalyst in step (3) is carried out at a temperature in the range of 150 to 350°C, preferably 200 to 330°C, more preferably 230 to 320°C, more preferably 250 to 315°C, more preferably 270 to 310°C, more preferably 280 to 305°C, and more preferably 290 to 300°C.

20. The method according to any one of embodiments 1 to 19, wherein the duration of contact of mixture (M1) with the catalyst in step (3) is in the range of 0.5 to 70 hours, preferably 1 to 50 hours, more preferably 3 to 40 hours, more preferably 5 to 35 hours, more preferably 10 to 30 hours, more preferably 15 to 25 hours, more preferably 18 to 23 hours, and more preferably 19 to 21 hours.

21. The method according to any one of the preceding claims, wherein the contacting of the mixture (M1) with the catalyst in step (3) and the recovery of the reaction mixture (M2) in step (4) are carried out in continuous and/or batch mode, preferably in batch mode.

22. The method according to any one of the preceding claims, wherein the method is carried out in continuous and/or batch mode, preferably in batch mode.

23. The method is
(5) The method according to any one of the preceding embodiments, further comprising separating the compound of formula (II) from the reaction mixture (M2) to obtain a mixture (M3) containing unreacted compound of formula (I) and/or unreacted ethylene.

24. The method is
(6) The process of embodiment 23, further comprising recycling the mixture (M3) containing unreacted compound of formula (I) and/or unreacted ethylene to step (1).

25. The method of any one of the preceding claims, wherein the zeolitic material having a BEA-type framework structure contained in the catalyst exhibits a SiO2:X2O3 molar ratio in the range of 10 to 200, preferably 15 to 150, more preferably 20 to 100, more preferably 25 to 70, more preferably 30 to 65, more preferably 35 to 60, more preferably 38 to 55 _, more preferably 40 to 50, and more preferably 42 to 46, wherein preferably _{the SiO2 : X2O3 molar} ratio of the framework structure is determined from elemental analysis or ^29Si MAS NMR of the zeolitic material, preferably from ^29Si MAS NMR of the zeolitic material.

26. The method according to any one of the preceding claims, wherein the trivalent element X of the zeolitic material having a BEA-type framework structure contained in the catalyst is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, and X is preferably Al.

27. The zeolitic material having a BEA-type framework structure contained in the catalyst exhibits an amount of Bronsted acid sites (BA) in the range of 100-900 μmol/g, preferably 150-700 μmol/g, more preferably 200-650 μmol/g, more preferably 350-600 μmol/g, more preferably 380-550 μmol/g, more preferably 410-500 μmol/g, more preferably 430-470 μmol/g, and more preferably 445-450 μmol/g;
27. The method of any one of the preceding embodiments, wherein the amount of Bronsted acid sites is determined by temperature programmed desorption of ammonia (NH3-TPD) or ³¹ P MAS NMR using trimethylphosphine oxide.

28. The zeolitic material having a BEA-type framework structure contained in the catalyst exhibits an amount of Lewis acid sites (LA) in the range of 100-350 μmol/g, preferably 110-300 μmol/g, more preferably 120-280 μmol/g, more preferably 140-260 μmol/g, more preferably 150-240 μmol/g, more preferably 160-220 μmol/g, more preferably 170-200 μmol/g, and more preferably 180-190 μmol/g;
28. The method of any one of the preceding embodiments, wherein the amount of Lewis acid sites is determined by temperature programmed desorption of ammonia (NH3-TPD) or ³¹ P MAS NMR using trimethylphosphine oxide.

29. The catalyst comprises a zeolitic material having a BEA-type framework structure, the BA:LA ratio of the amount of Bronsted acid sites (BA) to the amount of Lewis acid sites (LA) being in the range of 0.5 to 8, preferably 1 to 5, more preferably 1.3 to 4, more preferably 1.6 to 3.4, more preferably 1.8 to 3, more preferably 2.0 to 2.7, more preferably 2.2 to 2.6, and more preferably 2.3 to 2.5;
29. The method of any one of the preceding claims, wherein the amount of Bronsted acid sites and Lewis acid sites, respectively, is determined by temperature programmed desorption of ammonia (NH3-TPD) or by ^31P MAS NMR using trimethylphosphine oxide.

30. The method of any one of the preceding embodiments, wherein the BET surface area of the zeolitic material having a BEA-type framework structure contained in the catalyst, as determined by ISO 9277:2010, is in the range of 350-800 m ² /g, preferably ^400-700 m ² /g, more preferably 430-650 m ² /g, more preferably 450-600 m ² /g, more preferably 460-550 m ² /g, more preferably 470-530 m ² /g, more preferably 480-520 m ² /g, and more preferably 490-510 m 2 /g.

31. The total pore volume of the zeolitic material having a BEA-type framework structure contained in the catalyst, as determined by nitrogen adsorption from the BJH method, is in the range of 0.3-0.5 cm 3 /g, preferably 0.31-0.45 cm ³ /g, more preferably 0.32-0.42 cm ³ /g, more preferably 0.33-0.4 cm ³ /g, more preferably 0.34-0.39 cm ³ /g, more preferably 0.35-0.38 cm ³ /g, and more preferably 0.36-0.37 cm ³ /g;
31. The method according to any one of the preceding embodiments, wherein the total pore volume is preferably determined according to DIN 66134.

32. A synthetic method that does not use organic templates
(A) preparing a mixture comprising one or more sources of _SiO2 , one or more sources of _X2O3 , and seed crystals, the seed crystals comprising one or more _zeolitic materials having a BEA-type framework structure;
(B) crystallizing the mixture obtained in step (A) to obtain a zeolitic material having a BEA-type framework structure,
32. The method of any one of the preceding claims, wherein X is a trivalent element, and the mixture prepared in step (A) and crystallized in step (B) does not contain an organic template as a structure directing agent.

33. The method according to any one of the preceding claims, wherein the mixture prepared in step (A) and crystallized in step (B) contains 5% by weight or less of carbon, calculated as the element and based on 100% by weight of SiO ₂ contained in the mixture, preferably 1% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, more preferably 0.05% _by weight or less, more preferably 0.01% by weight or less, more preferably 0.005% by weight or less, more preferably 0.001% by weight or less, more preferably 0.0005% by weight or less, and more preferably 0.0001% by weight or less, calculated as the element and based on 100% by weight of SiO 2 contained in the mixture.

34. The method according to any of embodiments 32 or 33, wherein the zeolitic material having a BEA-type framework structure obtained in step (B) comprises one or more alkali metals M, where M is preferably selected from the group consisting of Li, Na, K, Cs, and combinations of two or more thereof, more preferably from the group consisting of Li, Na, K, and combinations of two or more thereof, more preferably the alkali metal M is Na and/or K, more preferably Na.

35. The method of embodiment 34, wherein the molar ratio M: _SiO2 in the mixture prepared in step (A) and crystallized in step (B) ranges from 0.05 to 5, preferably from 0.1 to 2, more preferably from 0.3 to 1, more preferably from 0.4 to 0.8, more preferably from 0.45 to 0.7, more preferably from 0.5 to 0.65, and more preferably from 0.55 to 0.6.

36. The method according to any one of embodiments 32 to 35, wherein the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) comprise one or more silicates, preferably one or more alkali metal silicates, where the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb, and Cs, more preferably the alkali metal is Na and/or K, and more preferably the alkali metal is Na, and more preferably the one or more sources of SiO ₂ contained in the mixture prepared in step (A) and crystallized in step (B) comprise water glass, preferably sodium silicate and/or potassium silicate, more preferably sodium silicate.

37. The method of any one of embodiments 32 to 36, wherein the one or more sources of _SiO2 contained in the mixture prepared in step (A) and crystallized in step (B) further comprises one or more silicas, preferably one or more silica hydrosols and/or one or more colloidal silicas, and more preferably one or more colloidal silicas.

38. The method of any one of embodiments 32 to 37, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof, and X is preferably Al.

39. The method according to any one of embodiments 32 to ₃₈ , wherein the one or more sources of _X2O3 contained in the mixture prepared in step (A) and crystallized in step (B) comprise one or more aluminate salts, preferably aluminates of alkali metals, where the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb, and Cs, more preferably the alkali metal is Na and/or K, and more preferably the alkali metal is Na.

40. The method of any one of embodiments 32 to 39, wherein the molar ratio SiO ₂ :X ₂ O ₃ of the mixture prepared in step (A) and crystallized in step (B) is in the range of 1 to 200, preferably 5 to 100, more preferably 10 to 50, more preferably 15 to 40, more preferably 20 to 30, more preferably 23 to 25, and more preferably 23.5 to 24.

41. The method of any one of embodiments ₃₂ to 40, wherein the amount of seed crystals contained in the mixture prepared in step ( _A ) and crystallized in step (B) is in the range of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, more preferably 1.5 to 5% by weight, more preferably 2 to 4% by weight, and more preferably 2.5 to 3.5% by weight, calculated as SiO2 based on 100% by weight of the one or more sources of SiO2 in the mixture.

42. The method according to any one of embodiments 32 to 41, wherein the mixture prepared in step (A) and crystallized in step (B) further comprises one or more solvents, wherein the one or more solvents preferably comprise water, more preferably deionized water, and wherein more preferably water, preferably deionized water, is used as the solvent further comprised in the mixture prepared in step (A) and crystallized in step (B).

43. The method of embodiment 42, wherein the molar ratio H ₂ O:SiO ₂ of the mixture prepared in step (A) and crystallized in step (B) ranges from 5 to 100, preferably from 10 to 50, more preferably from 13 to 30, more preferably from 15 to 20, and more preferably from 17 to 18.

44. The method of any one of embodiments 32 to 43, wherein the crystallization in step (B) involves heating the mixture, preferably the temperature of the heating is in the range of 80 to 200°C, more preferably 90 to 180°C, more preferably 100 to 160°C, more preferably 110 to 140°C, and more preferably 115 to 130°C.

45. The method according to any one of embodiments 32 to 44, wherein the crystallization in step (B) is carried out under autogenous pressure, preferably under solvothermal conditions, and more preferably under hydrothermal conditions.

46. The method of embodiment 44 or 45, wherein in step (B) the mixture is heated for a period ranging from 5 to 200 hours, preferably from 20 to 160 hours, more preferably from 60 to 140 hours, and more preferably from 100 to 130 hours.

47. An organic template-free synthetic method for preparing zeolitic materials having a BEA-type framework structure is disclosed,
(C) isolating the zeolitic material having a BEA-type framework structure obtained in step (B), preferably by filtration, and (D) optionally washing the zeolitic material having a BEA-type framework structure obtained in step (B) or (C), preferably in step (C), and/or
(E) optionally drying the zeolitic material having a BEA-type framework structure obtained in step (B), (C) or (D), preferably in step (D),
47. The method according to any one of embodiments 32 to 46, wherein steps (C) and/or (D) and/or (E) can be performed in any order, and wherein one or more of said steps are repeated, preferably one or more times.

48. An organic template-free synthetic method for preparing zeolitic materials having a BEA-type framework structure is disclosed in
(F) in step (C), (D) or (E), exchanging one or more ionic non-framework elements contained in the zeolitic material with BEA-type framework structure preferably obtained in step (E) for H ⁺ and/or NH ₄ ⁺ , preferably for NH ₄ ⁺ ; and/or (G) preferably drying and/or calcining, preferably drying and calcining, the zeolitic material with BEA-type framework structure obtained in step (C), (D), (E) or (F),
48. The method according to embodiment 47, wherein steps (F) and/or (G) are preferably repeated one or more times, preferably 1 to 3 times, more preferably 1 or 2 times, and more preferably once.

49. An organic template-free synthetic method for preparing zeolitic materials having a BEA-type framework structure is disclosed in
(H) in step (C), (D), (E), (F) or (G), preferably treating the zeolitic material having a BEA-type framework structure obtained in step (G) with an aqueous solution having a pH of at most 5, and (I) isolating the zeolitic material having a BEA-type framework structure obtained in step (H), preferably by filtration, and/or
(J) optionally washing the zeolitic material having a BEA-type framework structure obtained in step (H) or (I), preferably in step (I), and/or
(K) optionally drying and/or calcining, preferably drying, the zeolitic material having a BEA-type framework structure obtained in step (H), (I) or (J), preferably in step (J);
The method according to embodiment 47 or 48, wherein steps (I) and/or (J) and/or (K) can be performed in any order, and wherein one or more of said steps are preferably repeated one or more times, preferably 1 to 3 times, more preferably 1 or 2 times, and more preferably once.

50. The method of embodiment 49, wherein the pH of the aqueous solution used to treat the zeolitic material in step (H) is in the range of -1.5 to 3, preferably -1.2 to 2, more preferably -1 to 1.5, more preferably -0.8 to 1, more preferably -0.6 to 0.7, more preferably -0.5 to 0.5, more preferably -0.3 to 0.3, more preferably -0.2 to 0.2, and more preferably -0.1 to 0.1.

51. The method of embodiment 49 or 50, wherein in step (H) the zeolitic material is treated with an aqueous solution of a mineral acid, wherein the concentration of the mineral acid in the solution is in the range of 0.05 to 4 M, preferably 0.1 to 3 M, more preferably 0.2 to 2.5 M, more preferably 0.4 to 2 M, more preferably 0.6 to 1.5 M, more preferably 0.8 to 1.2 M, and more preferably 0.9 to 1.1 M.

52. The method according _to embodiment 51, wherein the mineral acid is selected from the group consisting of HF, _HCl , HBr, _HNO3 , _H3PO4 , _{H2SO4 , H3BO3} , _HClO4 , and mixtures of two or more thereof, preferably from the group consisting of HCl, _{HBr, HNO3, H2SO4 , HClO4 ,} and mixtures of two or more thereof, more preferably from the group consisting of HCl, _{HNO3 , H2SO4} , and mixtures of two or more thereof, more preferably the mineral acid is HCl and/or _HNO3 , preferably _HNO3 .

53. The method of any one of embodiments 49 to 52, wherein in step (H) the zeolite material is added to the aqueous solution and the mixture is heated at a temperature preferably in the range of 30 to 100°C, more preferably 35 to 90°C, more preferably 40 to 80°C, more preferably 45 to 75°C, more preferably 50 to 70°C, and more preferably 55 to 65°C.

54. The method of any one of embodiments 49 to 52, wherein in step (H), the zeolite material is added to the aqueous solution and the mixture is treated at a temperature in the range of 5 to 40°C, more preferably 10 to 35°C, more preferably 15 to 30°C, more preferably 17 to 25°C, more preferably 19 to 23°C, and more preferably 20 to 22°C.

55. The method of any one of embodiments 49 to 54, wherein in step (H), the mixture is treated for a period in the range of 0.1 to 10 hours, preferably 0.1 to 7 hours, more preferably 0.5 to 5 hours, more preferably 0.5 to 4.5 hours, more preferably 1 to 4 hours, more preferably 1 to 3.5 hours, more preferably 1.5 to 3 hours, and more preferably 1.5 to 2.5 hours.

56. The method of any one of embodiments 47 to 55, wherein the drying in steps (E) and/or (G) and/or (K), preferably in steps (E), (G) and (K), is carried out at a temperature in the range of 80 to 200°C, more preferably 90 to 180°C, more preferably 100 to 160°C, more preferably 110 to 140°C, and more preferably 115 to 130°C.

57. The method according to any one of embodiments 47 to 56, wherein the drying in step (E) and/or (G) and/or (K), preferably in step (E), (G) and (K), is carried out for a period in the range of 1 to 120 hours, preferably 5 to 96 hours, more preferably 8 to 72 hours, more preferably 10 to 60 hours, more preferably 12 to 48 hours, more preferably 14 to 42 hours, more preferably 16 to 36 hours, more preferably 18 to 30 hours, more preferably 20 to 24 hours, and more preferably 21 to 23 hours.

58. The method of any one of embodiments 48 to 57, wherein the calcination in step (G) and/or (K), preferably in step (G), is carried out at a temperature in the range of 250 to 1,000°C, preferably 300 to 900°C, more preferably 350 to 850°C, more preferably 400 to 800°C, more preferably 450 to 750°C, more preferably 500 to 700°C, and more preferably 550 to 650°C.

59. The method of any one of embodiments 48 to 58, wherein the calcination in step (G) and/or (K), preferably in step (G), is carried out for a period in the range of 0.5 to 36 hours, more preferably 1 to 24 hours, more preferably 1.5 to 18 hours, more preferably 2 to 12 hours, more preferably 2.5 to 9 hours, more preferably 3 to 7 hours, more preferably 3.5 to 6.5 hours, more preferably 4 to 6 hours, and more preferably 4.5 to 5.5 hours.

60. The method of any one of embodiments 32 to 59, wherein the zeolitic material having a BEA-type framework structure formed in step (B) comprises zeolite beta, preferably wherein the zeolitic material having a BEA-type framework structure formed in step (B) is zeolite beta.

61. The method according to any one of embodiments 32 to 60, wherein the seed crystals contained in the mixture prepared in step (A) and crystallized in step (B) comprise a zeolitic material having a BEA-type framework structure, preferably zeolite beta, and more preferably a zeolitic material having a BEA-type framework structure that can be obtained and/or is obtained by an organic template-free synthesis method for the production of a zeolitic material having a BEA-type framework structure as defined in any one of embodiments 32 to 59.

FIGURE 1 shows the reaction scheme in which 2,5-dimethylfuran (2,5-DMF) undergoes a Diels-Alder cycloaddition reaction with ethylene to a cycloaddition intermediate that is converted to p-xylene upon elimination of water. The major side reactions of further alkylation to 3-methyl-cyclopentanone and to 1-n-propyl-4-methylbenzene are also shown.

Figure 2 shows the reaction scheme where 2-methylfuran undergoes Diels-Alder cycloaddition of ethylene to a cycloaddition intermediate that is converted to toluene with elimination of water. Also shown are the major side reactions to oligomers, isomerization of the cycloadduct to epoxides, further alkylation of the product to 1-ethyl-4-methylbenzene, and dimerization to oligomers.

Figure 3 shows the reaction scheme in which furan undergoes Diels-Alder cycloaddition of ethylene to a cycloaddition intermediate that is converted to benzene with elimination of water. Major side reactions are also shown: dimerization to oligomers, isomerization of the cycloadduct to ketones, and further alkylation to ethylbenzene.

Figure 4 shows the reaction products and selectivities for the conversion of 2,5-dimethylfuran and ethylene over zeolite beta catalysts for Reference Example 1 (Si/Al=7), Reference Example 2 (Si/Al=22), Reference Example 3 (Si/Al=36), and commercial zeolite beta (Si/Al=19). The figure shows the conversion, selectivity to p-xylene and the alkylation product 1-n-propyl-4-methylbenzene, and the yield of p-xylene (indicated by "★") in %.

Figure 5 shows the reaction products and selectivities for the conversion of ethylene to 2,5-dimethylfuran (2,5-DMF), 2-methylfuran (2-MF), and furan, respectively, over the zeolite beta catalyst according to Reference Example 2 (Si/Al=22). The figure shows the conversion, the selectivity to p-xylene and by-products (alkylated and isomerized by-products and oligomers), and the yield of p-xylene (denoted by "★") in %.

Experimental Section Porosity Determination Surface area, pore volume and pore size distribution were determined by _N2 adsorption/desorption experiments on a Micromeritics ASAP-2020 analyzer at −196° C. Before each measurement, the samples were outgassed at 400° C. and <10 ⁻³ Pa for 6 h.

Temperature programmed ammonia desorption (NH ₃ -TPD) and acidity determination Temperature programmed NH ₃ desorption (NH ₃ -TPD) was performed using a chemisorption analyzer (FINETECH, Finesorb3010C, China) and the exhaust gas was detected using a TCD. Before the measurement, the samples were pretreated with He flow at 500°C and cooled to the desired temperature. 5000 ppm NH ₃ in He (100 ml/min) was introduced at 100°C for 0.5 h, followed by purging with He for 1.5 h, after which the temperature was increased from 100 to 700°C at a rate of 10°C/min.

After deconvolution of the temperature programmed _NH3 desorption (TPD) profiles, all samples showed three desorption peaks centered at about 200°C (low temperature), 250°C (medium temperature), and 340°C (high temperature), respectively. The latter two peaks could be roughly attributed to _NH3 desorption at strong and weak Brønsted acid sites (BA), while the low temperature peak could be attributed to _NH3 desorption at Lewis acid sites (LA). Based on this, the respective amounts of Brønsted (BA) and Lewis (LA) acid sites, and the B/L ratio were calculated by integration of the desorption signals.

^31P MAS NMR measurements and acidity determination using TMPO All solid-state magic angle spinning (MAS) NMR experiments were performed on an Agilent DD2-500MHz spectrometer. ^31P MAS NMR single pulse spectra were measured at 202.3MHz, speed 14kHz, π/4 excitation pulse _1.2μs , with a recycle delay of 10s. Chemical shifts were referenced to 85% _H3PO4 .

To better understand the acidity and strength of H-Beta zeolites with various Si/Al ratios, ^31P MAS NMR experiments were performed, which is an effective tool to investigate the acidic properties using trimethylphosphine oxide (TMPO) as a probe molecule. In addition to being able to distinguish the types of acid sites (Bronsted or Lewis acid), the ^31P -TMPO MAS NMR approach is also useful in identifying the Bronsted acid strength of the zeolite catalysts, which can cover the full range from weak, medium, strong to super acidic.

For quantitative measurements of acidity, the mass of all samples was measured and the spectra were calibrated by measuring a known amount of ( _NH4 ) _2HPO4 , which was performed under the same conditions except for a longer ₉₀ s pulse delay. For the adsorption of trimethylphosphine oxide (TMPO, 99%, alpha) during the preparation of the samples for measurement, the samples were first completely dehydrated under vacuum for 20 h. Then, a known amount of TMPO dissolved in _{anhydrous CH2Cl2} was introduced into the vessel containing the dehydrated solid samples in _N2 atmosphere and evacuated at about 50 °C to remove _{the CH2Cl2} solvent. To ensure uniform adsorption of the probe molecules on the zeolite, they were further subjected to a heat treatment at 165 °C for 1 h. Finally, the samples were transferred to the NMR rotor and then sealed with an airtight end cap in a _N2 glove box.

After deconvolution of ^{the 31} P MAS NMR, seven peaks appeared from downfield to upfield. In addition to physisorbed TMPO at about 43 ppm, ^{the 31} P NMR chemical shifts from 50 to 84 ppm were attributed to chemisorbed TMPO on Bronsted or Lewis acid sites. More specifically, the peaks at about 83, 69, and 55-62 ppm were assigned to TMPO adsorbed on the strongest, medium, and weakest Bronsted acid sites, respectively, and the peaks at 65 and 50 ppm were assigned to TMPO adsorbed on Lewis acid sites. Based on the classification, the total amount of Bronsted acid (BA) and Lewis (LA) acid sites was quantified, and the B/L ratio was calculated based on the obtained values.

^29Si MAS NMR Measurements All solid-state magic angle spinning (MAS) NMR experiments were performed on an Agilent DD2-500MHz spectrometer. ^29Si MAS NMR spectra were collected using a 6mm MAS probe at 99.3MHz at a speed of 4kHz, 400 scans, and a 4s recycle delay. Chemical shifts were referenced to sodium 4,4-dimethyl-4-silapentanesulfonate (DSS).

The Si/Al molar ratio in the framework of each material was determined by deconvolution of the corresponding ²⁹ Si MAS NMR spectrum.

Reference Example 1: Synthesis of H-BEA without organic template 12.693 kg of distilled water was placed in a 60 L autoclave equipped with stirring means. 0.955 kg of _NaAlO2 was dissolved in 5 L of distilled water and added to the water in the autoclave with stirring. Next, 21.447 kg of sodium water glass (26% by weight _SiO2 , 8% by weight _Na2O , and 66% by weight _H2O ) was added with stirring, causing the viscosity of the mixture to increase sharply and then decrease again. Then, 3.762 kg of Ludox® AS40 (40% by weight _SiO2 and 60% by weight _H2O ) were added and the resulting gel was stirred at 200 rpm for 3 hours, after which 0.717 kg of a suspension of zeolite Beta species (commercially available from Zeolyst International, Inc., Valley Forge, PA19482, USA, under the trade name CP814C, CAS registration number 1318-02-1, converted to H-form by calcination at 550°C for 5 hours (a heating ramp of 1°C/min was used to obtain the calcination temperature)) was added in 1 L of distilled water with stirring at 100 rpm. The mixture thus obtained contained an aluminosilicate gel with a molar ratio of 1.00 SiO ₂ : 0.0422 Al ₂ O ₃ : 0.291 Na ₂ O : 17.50 H ₂ O. The reaction mixture was heated to a temperature of 120° C. in 3 hours with stirring at 100 rpm using a constant heating ramp, and then said temperature was maintained for 60 hours with the same stirring speed. After cooling the reaction mixture to room temperature, the solid was separated by filtration, washed repeatedly with distilled water, and then dried at 120° C. for 16 hours to obtain Na zeolite beta. X-ray diffraction of the product confirmed the BEA-type framework structure of the obtained crystalline material. The obtained white crystalline material showed a crystallinity of 93% at 2° theta in the range of 18-25°, compared to that of zeolite beta seed material (CP814C from Zeolyst).

1,000 g of distilled water was placed in a 2 L reaction vessel. Then, 125 g of ammonium nitrate and 125 g of Na-zeolite beta obtained according to Reference Example 1 were added to the mixture via a funnel, which was then rinsed with 125 g of distilled water. The resulting suspension was then heated to 80° C. and kept at this temperature with continuous stirring for 2 hours. The solids were filtered and then the filter cake was washed with distilled water until the conductivity of the wash water was less than 20 microsiemens/cm. The filter cake was dried overnight at 120° C. to obtain 138.5 g of zeolite beta in its ammonium form. This procedure was repeated with an additional 125 g of Na-zeolite beta from Reference Example 1 to obtain an additional 131.5 g of zeolite beta in its ammonium form. Finally, 236 g of zeolite beta in its H form was obtained by calcining both batches at 500° C. for 5 hours (heating increase 2 K/min).

1,000 g of distilled water was placed in a 2 L reaction vessel. Next, 118 g of ammonium nitrate from the first ammonium ion exchange procedure and 118 g of H-zeolite beta were added to the mixture via a funnel, which was then rinsed with 118 g of distilled water. The resulting suspension was then heated to 80° C. and held at this temperature with continuous stirring for 2 hours. The solids were filtered and then the filter cake was washed with distilled water until the conductivity of the wash water was less than 10 microSiemens/cm. The filter cake was dried at 120° C. overnight to obtain 111 g of zeolite beta in its ammonium form. This procedure was repeated with 125 g of ammonium nitrate from the first ammonium ion exchange procedure and an additional 125 g of H-zeolite beta, thus obtaining an additional 110 g of zeolite beta in its ammonium form. Samples of H-zeolite beta were combined and a 65 g sample was subjected to a calcination step at 750° C. for 5 h (heat increase 2 K/min) to obtain 59.5 g of zeolite beta in its H form. The Si:Al molar ratio of H-zeolite beta was 7 as determined from its ²⁹ Si MAS NMR spectrum.

Reference Example 2: Dealumination of H-BEA obtained from synthesis without organic template 1,250 ml of a 1 M solution of nitric acid was placed in a beaker equipped with a stirrer. 25 g of H-zeolite beta obtained from Reference Example 1 was added and the mixture was stirred at room temperature for 2 hours. The solid was filtered off and washed with distilled water until the conductivity of the wash water was 165 microSiemens/cm. The solid was then dried overnight at 120°C to obtain 23.7 g of zeolite beta, where elemental analysis gave a Si:Al mass ratio of 40:2.6. The Si:Al molar ratio of the dealuminated zeolite beta determined from the ^29Si MAS NMR spectrum was 22.

Reference Example 3: Dealumination of H-BEA obtained from synthesis without organic templates 1,219 ml of a 1 M solution of nitric acid was placed in a beaker equipped with a stirrer. 24.38 g of H-zeolite beta obtained from Reference Example 1 was added and the mixture was stirred at room temperature for 5 hours. The solid was filtered off and washed with distilled water until the conductivity of the wash water was 65 microSiemens/cm. The solid was then dried overnight at 120°C to give 21.4 g of zeolite beta, where elemental analysis gave a Si:Al mass ratio of 40:2.1. The Si:Al molar ratio of the dealuminated zeolite beta determined from the ^29Si MAS NMR spectrum was 36.

Example 1: Synthesis of aromatic compounds Catalytic conversion of 2,5-dimethylfuran, 2-methylfuran, or furan with ethylene was carried out in a 50 ml stainless steel autoclave. Prior to the reaction, the autoclave was purged with nitrogen, then 0.3 g of H-beta zeolite was placed in the reactor, and the desired amount of 2,5-dimethylfuran, 2-methylfuran, or furan was transferred to the autoclave with the solvent. More specifically, a 1.56 M solution of the respective compound in heptane was used. The reactor was then pressurized with ethylene gas, and the mixture was stirred at 1000 rpm using a mechanical stirrer to ensure easy mass transfer in the system and heated to the final temperature. In the reaction, the molar ratio of ethylene to 2,5-dimethylfuran was 0.18, the molar ratio of ethylene to 2-methylfuran was 0.18, and the molar ratio of ethylene to furan was 0.16.

After the reaction, the liquid product and the solid catalyst were separated by centrifugation. The products were analyzed using a gas chromatograph (Shimadzu, GC-2014C) equipped with a 30 m HP-5 capillary column and a flame ionization detector. The products were identified based on the retention times and response factors of standard chemicals and quantified using a known amount of n-decane as an external standard. The products were further identified by GC/MS (Agilent, HP6890/5973MSD) equipped with a 30 m HP-5MS column.

For comparison, a commercial zeolite beta with Si/Al=19 from organotemplate-mediated synthesis (CP814C, _NH4 ⁺ form, Zeolyst) was converted to the H ⁺ form by calcination at 550° C. for 4 h and then used in the comparative test runs. The Si:Al molar ratio of the commercial zeolite beta was 19 as determined from its ^29Si MAS NMR spectrum.

The properties of the zeolite beta catalyst used in the test experiments are given in Table 1. In particular, the molar ratio of Si:Al determined from ^29Si MAS NMR spectra, the ratio of the amount of Brønsted acid sites (BA) to the amount of Lewis acid sites (LA) determined by temperature programmed ammonia desorption (NH ₃ -TPD) and by ^31P MAS NMR using trimethylphosphine oxide, respectively, the absolute amount of Brønsted acid sites and Lewis acid sites by NH ₃ -TPD, and the BET surface area and total pore volume are given.

Table 1: Characteristics of the zeolite beta catalyst used in the test experiments

The results of a comparative test of various zeolite beta catalysts in the reaction of 2,5-dimethylfuran with ethylene are shown in Figure 4. The reaction was carried out at 300°C for 20 hours, and the reactor was pressurized with ethylene before the reaction to obtain an initial pressure of 4.0 MPa before heating. Thus, as can be seen from the results, quite unexpectedly, it was found that the conversion on zeolite beta obtained from synthesis without organic templates is substantially higher than that of commercial zeolite beta obtained from template synthesis. In particular, as can be seen from the results, it was found that, very surprisingly, the higher conversion is not related to the Si/Al molar ratio, but that the improved results of the catalysts used in the process of the invention result from the fact that they are obtained from a synthesis method without organic templates. Thus, as can be seen from the results obtained using zeolite beta samples obtained from synthesis without organic templates, which exhibit Si/Al molar ratios of 7 and 22, respectively, it was found that both exhibit substantially higher conversions than commercial zeolite beta obtained from template synthesis, which has a Si/Al molar ratio of 19, i.e. between the aforementioned Si/Al molar ratios.

In addition to the aforementioned tests, the zeolite beta from Reference Example 2 was used to react ethylene with 2,5-dimethylfuran, 2-methylfuran, and furan, respectively. The results are shown in Figure 5. The reaction pathways to the desired aromatic products and the major by-products by Diels-Alder cycloaddition reaction and subsequent removal of water are shown in Figures 1-3. As can be seen from the results shown in Figure 5, in the reaction of 2,5-dimethylfuran, the conversion to the desired products and the selectivity of the reaction are nearly 100%, respectively, while the conversion and selectivity were significantly reduced when ethylene was reacted with 2-methylfuran and furan, respectively.

List of cited references - US2013/0245316A1
- Ni, L. et al. ChemSusChem 2017, 10, 2394
- Chang, C. - C. et al. Green Chem. 2014, 16, 585
- Cho, H. J. et al. ChemCatChem 2017, 9, 398

Claims (12)

A method for producing an aromatic compound, comprising the steps of:
(1) Ethylene and formula (I)

preparing a mixture (M1) comprising a compound of
(2) feeding the mixture (M1) into a reactor containing a catalyst, the catalyst comprising a zeolitic material having a BEA-type framework structure;
(3) reacting at least a portion of the mixture (M1) to form a compound represented by formula (II)

contacting the mixture (M1) with the catalyst in the reactor to obtain aromatic compounds of
(4) recovering the reaction mixture (M2) containing the aromatic compound of formula (II) from the reactor;
Including,
wherein R ¹ and R ² are each independently H or a substituted or unsubstituted (C ₁ -C ₃ ) alkyl; and the zeolitic material with a BEA-type framework structure contained in the catalyst is obtained by a synthesis method without using an organic template;
The organic template-free synthesis method comprises:
(A) preparing a mixture comprising one or more sources of _SiO2 , one or more sources of _X2O3 , and seed crystals, the seed crystals comprising one or more _zeolitic materials having a BEA-type framework structure;
(B) crystallizing the mixture obtained in step (A) to obtain a zeolitic material having a BEA-type framework structure,
wherein X is a trivalent element selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof;
the zeolitic material having a BEA-type framework structure contained in the catalyst exhibits a SiO ₂ :X ₂ O ₃ molar ratio in the range of 20 to 100, the SiO ₂ :X ₂ O ₃ molar ratio of the framework structure being determined from ²⁹ Si MAS NMR of the zeolitic material ;
the zeolitic material having a BEA-type framework structure in said catalyst has a BA:LA ratio of the amount of Bronsted acid sites (BA) to the amount of Lewis acid sites (LA) in the range of 1.6 to 3.4, wherein the amount of Bronsted acid sites and the amount of Lewis acid sites, respectively, are determined by temperature programmed ammonia desorption (NH ₃ -TPD);
The process, wherein said mixture prepared in step (A) and crystallized in step (B) does not contain an organic template as a structure directing agent. The zeolitic material having a BEA-type framework structure exhibits an X-ray diffraction pattern including at least the following reflections:

wherein 100% means the intensity of the highest peak in the 2θ range of 20-45° in the X-ray powder diffraction pattern; and wherein the BEA-type framework structure comprises _{SiO2 and X2O3} , where X is a trivalent element. The method according to claim 1 or 2, wherein the compound of formula (I) is selected from the group consisting of substituted or unsubstituted furan, 2-methylfuran, 2,5-dimethylfuran, and mixtures of two or more thereof. The method according to any one of claims 1 to 3, wherein the mixture (M1) prepared in step (1) and reacted in step (3) further contains a solvent system. The method according to any one of claims 1 to 4, wherein the compound of formula (I) and/or ethylene is derived from biomass. The method according to any one of claims 1 to 5, wherein in steps (2) and (3), the zeolite material having a BEA-type framework structure contained in the catalyst is H-type. 7. The method according to claim 1, wherein in step (2) and step (3), the zeolitic material having a BEA-type framework structure contained in the catalyst contains not more than 5% by weight of a metal AM, calculated as an element and based on 100% by weight of SiO2 contained in the framework structure of the _zeolitic material having a BEA-type framework structure, where the metal AM represents Na. 8. The method according to claim 1, wherein in step (2) and step (3), the zeolitic material having a BEA-type framework structure contained in the catalyst contains not more than 5% by weight of metal TM, calculated as element and based on 100% by weight of _SiO2 contained in the framework structure of the zeolitic material having a BEA-type framework structure, where the metal TM represents Pt, Pd, Rh, and Ir. 9. The method according to claim 1, wherein in step (2) and step (3), the zeolitic material having a BEA-type framework structure contained in the catalyst contains not more than 5% by weight of phosphorus, calculated as element and based on 100% by weight of _SiO2 contained in the framework structure of the zeolitic material having a BEA-type framework structure. The method according to any one of claims 1 to 9, wherein the contact of mixture (M1) with the catalyst in step (3) is carried out at a temperature in the range of 150 to 350°C. The method according to any one of claims 1 to 10, wherein the method is carried out in continuous and/or batch mode . 2. The method of claim 1, wherein the mixture prepared in step (A) and crystallized in step (B) contains not more than 5% by weight of carbon, calculated as element and based on 100% by weight of _SiO2 contained in the mixture.

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